Sulfonic derivatives of dithiocarbamic acid and method of making the same



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bsmvnms' or DITHIOCXRBAMic pr'o AND METHOD OF Wolf gang Giindel,. Drisseldorf-OberkassehlGermany, as-

;f signor to Dehydag, Deutsche Hydrierwerke, G.m.'b;H.,

Dusseldorf, Germany, a corporation of Germany No Drawing. Application January 4, 1956 Serial No. 557,422 I Claims priority, application Germany January 5, 1955 10 Claims. "C1. 260-455) V [Ifhis invention relates to sulfonic derivatives of dithiocarb'amic acid, especially dithiocarbamiciacid ester-N- 'alkylsulfonic acids, and a'me thod of making such com I- pounds.

7 "*I have discovered that novel derivatives of dithiocarbamic acid esters or salts thereof are obtained'by first reacting salts of amino-.alkanesulfonic acids which have at least one hydrogen atom attached to the nitrogen atom with carbon disulfide' in the presence of equimolar amounts of a strong base, and thereafter transforming the salts of dithiocarbamic acid-N-alkylsulfonic acids produced thereby into the corresponding .salts of dithiocarbamic acid ester-N-alkylsulfonic acids with the aid of an alkylating agent.

The compounds obtained in this manner may-be represented by 'the structural formula *R-N-R -S Y I 5 s=Cs-X wherein R 'is hydrogen or an alkyl, cycloalkyl or aryl radical,- R is a bivalent aliphatic radical, Y is a saltforming cation and X 'is an aliphatic, aliphatic-aromatic or aromatic radical. Rand R may also be branched or substituted radicals, and X may similarly be a substituted radical. In those cases where the substituent carried by radical X- is another sulfonic group, the compounds formed by the reaction in accordance with the present invention are of particular interest and have'the general 1 structural formula wherein R, R X and Y represent the radicals above indicated, and Z is a salt-forming cation identical to or different from. Y.

The production of these novel compounds is carried out in two steps; but. it .is not necessary to-isolate the reac- Patented Oct. 6,

and the like. In the case of those aminosulfonic acids which contain more than one amino group in the molecule, one grjboth of the amino groups can be caused to react inthe above-described manner with the carbon disulfide. The second phase of the process according to the present invention comprises the esterification of the dithiocarbamic acid salts produced in the first phase and lhaving the general structural formula i With'a' substituting agent. In the aboveformula Y and Z represent salt-forming cations, such as alkali metal atoms. Compounds 'Whichmay be used for this purpose are those which are customarily employed as substituting agents suchf as 'dimethylsulfate, diethylsulfate, or other sulfuric oi 'sulfonic acid esters, as well as compounds comprising suflicientlyreactive halogen atoms, such as methylio'dide, ethylbromide, 'allylchloride, benzylchloride, andrthe' like. In the .case of these .ami nosulfonic acids of the reaction aresub'stituting agents which contain sulfonic acid groups or form sulfonic acid groups. Examples of such substituting agents are salts of halogenated sulfonic acids, such as salts of bromoefhane-sulfonic acid or of halogenated arylsulfonic acids wherein the halogen atom has been made. more susceptible to substitution by the introduction of'anionic substituent on'the .aryl

tion product formed in the first step before proceeding with the second step. Therefore, the reaction accordingto my invention can actually be performed in a single uninterrupted pro'cedureydespite the fact that the components react in two distinct phases. In general, it is advantageous to performthe reaction in an aqueous medium, but the usual organic solvents, such aslower molecular alcohols and ketones, may also be used as the reaction medium, if desired. a

In the first phase of the reaction according to the presradical, for example 4-chloro-3-nitrobenzene-sulfonic acid. .Other substituting agents which may be used are sultones, such as propanesultone, 1,4-butanesultone or technical mixtures of 1,3- and 1,4-butanesultone, and the like. Thesecond phase of the process, as above set forth,

may also-be carried out in aqueous solution. In general;

relatively mild reaction conditions are suificient to bring about a -reaction between the various components, both I in the first and the second phase, and the reaction product cut invention, salts of N-alkyl N-cycloalkylor N- aralkyl-aminoalkanesulfonic acids are reacted with carbon disulfide in the presence of equimolar amounts of a strong base, such as sodium hydroxide or potassium hydroxide, preferably in'aqueous solution. This reaction takes place surprisingly smoothly if the reaction mixture is thoroughly agitated, either at room temperature or at a moderately, elevated, temperature, -,for example 4050 C. The reaction has gone .to completion when the carbon disulfide has gone completely into solution and the reaction mixturejs substantially clear and is recovered with good yields and without the formation ofappreciable quantities of undesirable side-products.

' when the reactionaccording to the present invention is carried out in an aqueous medium, the reaction productsoften precipitate in crystalline form from the reaction solutipn d u1ing the second phase, because many-'of the products are relatively insoluble in water Inthose 'cases' where the precipitation is incomplete or insuificient, the

warm solution obtained at the end of the second phase I j is filtered in the presence of charcoal, and the filtrate is evaporated to dryness. The residual salt is then recrystallizedfrom a suitable solvent, for example from a lower alcohol; orfrom alcohol-water mixtures. g "The resulting pure products are colorless-"and vodorless crystalline substances, which are more or 1658 S0111 ble in water and may be stored for indefinite periods of time without decomposition.

The novel compounds produced by the above-described reaction are useful for a number of purposes.- For example, they are very effective inhibitors and their use in that capacity is particularly advantageous in the treatment of metal surfaces with acid solutions where it is important to prevent even the slightest corrosive attack upon the metal. Similarly, the sulfonic dithiocarbamic acid derivatives disclosed herein are useful as anti-corrosion agents in general, as fungicides, as vulcanization accelerators, and especially as brighteners for electroplating baths, as described in co-pending application Serial No. 552,699, filed December 13, 1955.

The following examples will further illustrate the present invention and enable'others skilledin the art to understand the invention more 'completely. It is to be understood, however, that I do not intend to limit the invention to the particular examples given below.

' 19.5 parts by weight of the internal salt of 3-butylaIninop'ropane-1-sulfonic acid (V mol) having a melting point of 162 to 163 C. (producedfrom equivalent amounts of n-butylamine and propane sultone) were dissolved in 100 parts by volume of 2 N sodium hydroxide A mol). The resulting solution was admixed with 7.6 parts by weight of carbon disulfide mol) and vigorously stirred at room temperature'until all of the carbon disulfide had gone into solution, which required about 2 hours. After adding 12.6 parts by weight benzyl chloride A6 mol), the mixture was stirred for 8 additional hours. The butyl-dithiocarbamic acid-benzylester- N-propane-w-sodium sulfonate formed during this period is'difliculty soluble in the reaction mixture, which contains sodium chloride, and is therefore substantially completely precipitated in finely crystalline form during the.

reaction. 30.5 parts by weight of the salt corresponding to 84% of the theoretical yield were isolated and obtained in analytically pure form by recrystallization from 80% alcohol.

Example II I o,H,-j -on2 oH.oH.so3Ni S=OS'C1H5 Following the procedure ofthe preceding example, an aqueous solution of butyl-dithiosodium carbaminate- N-propane-w-sodium sulfonate was reacted gradually with 1 5.4 parts by weight of diethylsulfate A mol) accompanied by. stirring, while allowing the temperature to rise ton40 C. The solution became clear after about 30 minutes and then 50 parts by volume of 2 N sodium hydroxide A mol)"were added to neutralize the sulfuric acid formed during the reaction. Thereafter, the solution was evaporated to dryness under a hood with an adequate draft. The residue, a grayish crystalline substance, was first extracted with a small amount'of 'cold isopropyl alcohol to remove malodorous impurities and thereafterrecrystallized from 800 parts by volume of the same alcohol in order to separate the'sodium' sulfate formed during the reaction. The butyl-dithio carbamic acid-ethylester-N-propane-w-sodium sulfonate .was obtained with goodyields. It was a colorless, odorless salt which was readily soluble in water.

12.2parts byweight propane sultone A mol) were gradually added to asolution .of but-yl-dithiosodiumcarcordance with Example I, accompanied by stirring, while taking care that the temperature did not rise above 50' C. Thereafter, the mixture was stirred until it practically no longer reacted alkaline; it was finally evaporated to dryness on a water bath, as described in Example 11. 42 partsby weight of butyl-dithiocarbamic acid-N-S -bispropane-w-sodium sulfonate, corresponding to 9.6% of the theoretical yield, remained behind. It was a colorless compound. By recrystallization from 95% alcohol, it was obtained in a form which was very easily soluble in water.

Example IV C HnNOHr-CHOHg--SO' Na Working in close adherence to the procedure of the Example .V

S=C-SOH;CHg-CH -SO;Na I A'solution of 22.9 parts by weight of the internal salt of 3-berizyl-aminopropane-1-sul-fonic' acid mol) pro: duced from molar amounts of benzy'lamine and 1,3.- propane sultone, in 100 parts by volume of 2N sodium 7 hydroxide (25 mol) was vigorously stirred at room tem- 1 part methanol.

baminatefN propane-w sodium sul'fonatepreparcd in 253-. 7

perature, after adding 7.6 parts by weight carbon disulfide until the latter had gone completely into solution (about 1 hour). To the clear solution 12.2 parts by weight of l,3- propane sultone A mol) wereadded as described in Example 111, and the solution was stirred until the alkaline reaction had practically disappeared. There after, the solution was, if necessary, neutralized with dilute sulfuric acid and evaporated to dryness. The residue consisted of 47 parts by weight of N-benzyldithiocarbamic acid-N S-bis-propane-w-sodium sulfonate in virtually quantitative yields. This salt was very difficulty soluble in allorganic solvents with the exception of methanol, and very readily solublev in water. It was recrystallized from a mixture of 3 parts isopropanol and Example VI CH: C H-NC H2-CH3-CH2-S OgNa.

CHz-Cfiz S=C,S--CHZCHZOH7SQQNB. Proceeding according tothe preceding example, but

using 22.1 parts by weight of .the internal salt of 3-cyolohexylaminopropane-l-sulfonic acid A mol) instead of the .internal salt of 3-benzylaminopropane-l-sulfonic acid and an analogous separation"procedure, 44.0 partsby weight of Nmyclohexyl-dithiocarbamic acid-N-SPbis-propane-w-sodium sulfonate were obtained. This product was very difficult to purify by recrystallization .but was obtained analytically pure by dissolving it in 300 parts by volume of warm methyl alcohol and precipitating it therefrom in crystalline form with 1000 parts by volume of warm isopropyl alcohol.

Example VII A solution of 'N-benzyldit-hio'sodiumcarbaminate N;propane- -sodiumsulfonate, prepared according to theprocedure .of Example V from 22.9 parts by weight of the internal salt-of 3 benzylaniino-propane-l-sulfonic" acid 5 ($5 mol), was admixed with 12.6 parts by weight of benzyl chloride, and the mixture was vigorously stirred at room temperature. The N-benzyldithiocarbamic acidbenzylester-N-propane-w-sodium sulfonate formed thereby precipitated in crystalline form during the reaction and was separated from the reaction mixture by filtration after about 36 hours of stirring. 'Ihefilter cake was then dried on clay. 23.2 parts by welght, correspondmg to 55% of the theoretical yield of the salt, were obtained. For purposes of purification, the salt was recrystallized from a mixture of 1 part ethyl acetate and 3 parts isopropanol. V

Example VII S=CS--CHg-CH2CHg-SO3N8' CH -N-CHr-QHrGHz-SOgNai 122 parts by weight 1,3-propane sultone were added to a solution of 30 parts by weight ethylene diamine /2 mol) in 500 parts by volume of alcohol, while taking care that the temperature did not exceed 50 C. After stirring this mixture for about 30 minutes at its boiling point, it was allowed to cool. The internal salt of ethylene diamine-N,N-bis-propane-w-sulfonic acid precipitated very slowly at the beginning but more rapidlyas the solution cooled. The precipitate was then filtered ofi. For the purpose of purification the reaction product was recrystallized from 'a mixture composed of 30 parts methanol and 70 parts water. The crystalline product, which was only moderately soluble in water, had a melting point above 200 C. 10.4 parts of this salt (V mol) were admixed with 200 parts by volume of 2N sodium hydroxide ($4 mol) and 15.2 parts by weight of carbon disulfide @1 mol), as previously described, and the mixture was stirred until the carbon disulfide had passed completely into solution; i.e., after about 4 hours. 7 After gradually adding 24.8 parts by weight of 1,3-propane sultone mol) and keeping the temperature below 50 C., the mixture was stirred fora short period of time and thereafter evaporated to dryness. If necessary, the mixture was neutralized with a small amount of sulfuric acid prior to evaporation. The residue was ethylene-bis-dithiocarbamic acid-N-S-bis-propanew-sodium sulfonate; it was obtained with excellent yields. The product was thoroughly admixed with alcohol and then washed with alcohol on a vacuum filter; in this form it possessed the expected analytical values. The salt was very readily soluble in water but almost completely insoluble in all organic solvents.

While I have disclosed certain specific embodiments of my invention, it will be apparent to persons skilled in the art that various changes and modifications can be made without departing from the spirit of the invention or the scope of the appended claims.

I claim:

1. Compounds having the structural formula wherein R is selected from the group consisting of hydrogen, lower alkyl, cyclohexyl, monocyclic aryl and alkylamino radicals, R is a bivalent alkyl radical, X is selected from the group consisting of lower alkyl, monocyclic aryl and lower alkyl sulfonic acid radicals and Y is an alkali metal atom.

2. Compounds having the structural formula R-NR1SO;Y

s =os X wherein R is a lower alkyl radical, R is a bivalent lower alkyl radical, X is a lower aliphatic radical and Y is an alkali metal atom.

3. Compounds having the structural formula R--NR soaY s= SX wherein R is a butyl radical, R is a propyl radical, X

is a lower alkylsulfonic radical and Y is an alkali metal atom.

4. Compounds having the structural formula wherein R is selected from the group consisting of hydrogen, lower alkyl, cyclohexyl, monocyclic aryl and alkylamine radicals, R is a bivalent alkyl radical, X is selected from the group consisting of lower alkyl, monocyclic aryl, and lower alkyl sulfonic acid radicals, Y is an alkali metal atom and n is a whole number from 1 to 2.

5. The compound having the structural formula o,Hv--N--(0H2)s-s0 Na s=o-s-(oH, ,-so,Na 6. The compound having the structural formula 4 vN-( CHz)r-S OaNa s= S(OH -SO Na 7. The compound having the structural formula X is a propylsulfonic radical and Y is an alkali metal atom.

References Cited in the file of this patent UNITED STATES PATENTS 1,972,961 Tisdale Sept. 11, 1934 2,127,375 Bousquet Aug. 16, 1938 2,313,871 Hanford et a1. Mar. 16, 1943 2,491,772 Rudel Dec. 20, 1949 2,673,839 3 Kirshenbaum et al Mar. 30, 1954 FOREIGN PATENTS 427,641 Great Britain Apr. 29, 1935 628,397 Great Britain Aug. 29, 1949 OTHER REFERENCES Journal of the American Pharmaceutical Association, vol. XLIV, pages 310-313, Collins et a1.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Noo 2,907,786

October 6, 1959 Wolfgang Gb ndel Column 2', line 40, for read Espec "in the case of these aminos'ulfonio acids" for "Example ially important for the second phase column 5, line 13, VII", in italics, read Example VIII in italioso Signed and salad this 29th day of March 1960.,

(SEAL) Attest:

KARL E0 AXLINE TAttesting Officer ROBERT C. WATSON Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 2,907,786

October 6, 1959 Wolfgang Giindel- It is hereby certified that error appears in the -printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 40, for "in the case of these aminos'ulfonic acids" read Especiallgy" important for the second phase column 5, line 13 for "Example VII", in italics, read Example VIII i.t: ."-,'.lic,s

Signed and sealed this 29th day of March 1960.,

(SEAL) Attest:

KARL H AXLINE,

ROBERT C. WATSON Attesting Officer Commissioner of Patents 

1. COMPOUNDS HAVING THE STRUCTURAL FORMULA 